Process for preparing resinous compositions

ABSTRACT

A polyurethane composition comprising the reaction product of an acrylic polymer comprising: Component A A monomer having BOND AND FURTHER HAVING -OH, -CONH2,-CONHCH2OH or -CON(CH2OH)2 groups, Component B A monobasic or polybasic acid having a BOND, Component C An alkyl ester of an Alpha , Beta -unsaturated carboxylic acid, or a compound having a GROUP BUT WHICH IS FREE OF -OH, -COOH and ester groups, or COMPOUND FREE OF H2C=C such as the glycidyl ester of versatic acid; and a diisocyanate such as xylene diisocyanate or a prepolymer thereof.

United States Patent Masuda et al.

[4 1 June 20, 1972 [54] PROCESS FOR PREPARING RESINOUS COMPOSITIONS 72Inventors: lliromasa Mauda, Osaka; Eiiti Nkhigald,

Nishinomiya; Tomosuke Maeda, Osaka, all

of Japan [73] Assignee: Nippon Yushi Kabushiki Kaisha, Cheyodaku, Tokyo,Japan [22] Filed: Sept. 8, 1970 [2i] Appl. No.: 70,482

Related U.S. Application Data [62] Division of Ser. No. 717,440, March29, I968, abandoned.

[30] Foreign Application Priority Data April 3, 1967 Japan ..42/20762[52] U.S. Cl ..260/77.5 CR, 260/l5, 260/851 I [5 l Int. Cl. C08q 22/08[58] Field of Search ..260/77.5 CR

[56] References Cited UNITED STATES PATENTS 3,245,941 4/1966 Mayer et al..260/3l.6

Primary Examiner-Donald E. Czaja Assistant Examiner-M. J. WelshAttorney-Waters, Roditi, Schwartz & Nissen [57] ABSTRACT A polyurethanecomposition comprising the reaction product of an acrylic polymercomprising:

Component A A monomer having c =C v bond and further having 0H,

group but which is free of --OH, -COOH and ester groups, or

C7CH2 0 compound free of H C C such as the glycidyl ester of versaticacid; and a diisocyanate such as xylene diisocyanate or a prepolymerthereof.

4 Claims, No Drawings PROCESS FOR PREPARING RESINOUS COMPOSITIONSCROSS-REFERENCE TO RELATED APPLICATIONS This is a division of co-pendingapplication Ser. No. 717,440; filed Mar. 29, 1968 now abandoned.

DETAILED DESCRIPTION This invention relates to polyurethanes preparedfrom a resinous polymeric composition and a diisocyanate such as xylenediisocyanate or a prepolymer thereof.

Polyurethanes have heretofore been manufactured from an isocyanate orprepolymer thereof and a polymer or a prepolymer having a reactive-OHgroup by a reaction between the reactive-OH group and the NCO group ofthe isocyanate. Metaxylene diisocyanate O C N C H;

I NC

and prepolymers thereof are desirable because they lead to driable andnon-yellowing polyurethanes. However, while the diisocyanate andprepolymers are miscible with polyester resins, they are notsufficiently soluble in copoly-condensed resinous compositions, and thusthey can not provide uniform films.

The object of the present invention is to provide polyurethane foamsbased on resinous polymeric compositions which are miscible with xylenediisocyanate OCN and prepolymers thereof.

Another object of the present invention is to provide usefulpolyurethanes which are able to provide uniform coating.

The terms copolymers and copoly-condensates as herein used means (1)acrylic, vinyl and allyl compounds, either alone or a combination of twoor more such compounds, and (2) condensates of compounds (1) with amino,epoxy, and polyether compounds.

Coated films incorporating the polyurethanes according to the presentinvention have good resistance to chemicals, weathering andcontamination, with improvements in resistance to yellowing and chalkingupon outdoor exposure which have heretofore constituted major drawbacksof conventional polyurethane paints.

This invention is the reaction product of a resinous polymericcomposition and a diisocyanate. The resinous polymeric composition isprepared by copoly-condensating three components A, B and C as describedbelow, in the ratio of 0.5 70 percent of Component A, 0.5 50 percent ofComponent B, and 100 (A B) of Component C, all by weight.

COMPONENT A A compound having a bond and further having a OH,

--CONH2, -CONHCHZOH or CON(CH,OH)2 groups.

COMPONENT B An organic monobasic or polybasic acid having a C=C bond.

COMPONENT C An alkyl ester of an afi-unsaturated carboxylic acid, or acompound having a 4 group but which is free of OH, COOH,

and ester groups, or a H (3 CH,

compound which is free of H C C groups, such as the glycidyl ester ofVERSATlC acid.

2 More particularly said Component A may be selected from the group ofthe following compounds:

(wherein 'n=1 or 2, and 1n=0 or 1-10),

b. Glycidyl methacrylate, or acrylate. c. Acrylamide or methacrylamideor the methylol derivatives thereof.

d. Alkylene glycol monoacrylate or methacrylate such as ethylene glycolmonoacrylate, propylene glycol monoacrylate or the correspondingmethacrylatesj e. Glycol, glycerine, trimethylolethane,trimethylolpropane,

pentaerythritol, polypentaerythritol or polyether or such other compoundhaving a plurality of hydroxyl groups at least one of which is removedand the rest of the hydroxyl groups are replaced by acryl, methacryl orallyl groups. Component B may be selected from the group of followingcompounds:

Monobasic acids and polybas ic acids having a bond such as acrylic acid,methacrylic acid, itaconic acid,

group such as diglycidyls, glycidyl ester of VERSATIC acid (CARDURA E),triglycidyl cyanurate, tri-glycidyl isocyanate.

CARDURA E is represented by the formula where R,, R, and R are saturatedaliphatic radicals and have a total number of carbon atoms between sevenand nine.

A mixture of the Components A, B and C as enumerated above is subjectedto copoly-condensationby the use of a conventional peroxide or azo-typecatalyst. A solvent and the polymerization catalyst are added to themixture of monomers, and the whole mixture is reacted for 2 to 6 hoursunder reflux. The reaction is continued till the desired viscosity isattained, and then by adding a suitable amount of solvent there isprepared a product having suitable solid content.

The copolymer or copoly-condensate thus obtained is then used. in thepreparation of the instant polyurethanes. The copolymer orcopoly-condensate is used either alone or in combination with aprepolyrner thereof or in mixture with one or more epoxy resins orderivatives thereof, polyester resins modified with Cardura-E,polyether, acrylated, vinylated and allylated polyester resins,including alkyd resins and saturated or unsaturated polyesters, andamino resins such as unmodified, alcohol modified or allyl modifiedamino resins; unmodified melamine resins, modifiedv melamine resins,benzoguanamine resins and urea resins. The product may also be mixedwith a cellulose derivative such as cellulose acetate, cellulose acetatebutyrate or nitro-cellulose.

The products according to the present invention may be compounded withany diluent or pigment before use.

The polyurethane products of the invention may be applied to objects bybrushing, spraying, roller, dipping, electrostatic coating, flowing,etc. They are useful as surface coatings and protective coatings onwoodworks, metals, light metals, treated steel plates, leathers andskins, artificial leathers, rubbers, plastics, fibers, papers, bricks,concrete molding, colored slates, films, cans, etc. Other usefulapplications include printing inks and adhesives.

This invention will now be described more fully by the followingexamples, wherein all parts are by weight.

EXAMPLE 1 Xylol 30 50 parts, methyl methacrylate 15 parts, ethylacrylate 15 parts, ethyl hexyl acrylate 50 parts, butyl methacrylate l 1parts, 2-hydroxyethyl acrylate 5 parts, acrylic acid 4 parts and benzoylperoxide 0.4 1.5 parts were reacted at a temperature between 100 C. andthe boiling point of the mixture for 3 hours. A product having aviscosity of 1.5 to 8 stokes in a 50 percent solution (xylol butylacetate 50 parts/50 parts) was obtained.

EXAMPLE 2 Xylol 50 parts, ethyl acrylate 29 parts, butyl acrylate 29parts, styrene 5 parts, and 2-hydroxypropyl acrylate 26 parts, Cardura-E10 parts, methacrylic acid 1 part and azoisobutyronitrile 0.4 1.5 partswere reacted in the same manner as described in Example 1, and a producthaving a viscosity of 1.5 to 5 stokes in a 50 percent solution wasobtained.

EXAMPLE 3 Butyl acetate 30 parts, styrene parts, ethyl acrylate 19parts, butyl methacrylate 30 parts, 2-hydroxyethyl acrylate 12 parts,propylene glycol monoacrylate 10 parts, acrylic acid 10 parts andacrylamide 4 parts were reacted as described above and a product wasobtained which exhibited a viscosity of 2 to 7 stokes in a 50 percentsolution.

EXAMPLE 4 Xylol 30 parts, acrylonitrile 12 parts, ethyl acrylate 29parts, methyl methacrylate 30 parts, cyclohexyl methacrylate 10 parts,Z-hydroxypropyl acrylate 10 parts, glycidyl methacrylate 1 part andmaleic anhydride 4 parts were reacted in the same manner as in ExampleI, and a product having a viscosity of 14 to 20 stokes in a 50 percentsolution was obtained.

EXAMPLE 5 Xylol 30 parts, styrene 30 parts, trimethylol propanediallylether 10 parts, diallyl maleate 20 parts, methyl methacrylate39.5 parts, methacrylic acid 0.5 part, and benzoyl peroxide 0.5 partwere reacted for 3 to 7 hours. A product having a viscosity of 3 to 7stokes was obtained.

EXAMPLE 6 One hundred parts of the copolymer obtained in accordance withExample 1, 20 parts of a prepolyrner of xylene diisocyanate, and 20parts of butyl acetate were mixed and the mixture was applied to a glassplate. After 20 minutes, this coating was dry to the touch and cured toa hard film in 4 hours at room temperature of 20 C. and humidity of 75percent.

EXAMPLE 7 One hundred parts of the copolymer obtained in Example 1, 35parts of a prepolyrner of xylene diisocyanate and 20 parts of ethylacetate were mixed and applied to a glass plate. Under the same dryingconditions as above, the coated film can be dried to finger touchdryness after 30 minutes and cured hard for 5 hours.

EXAMPLE 8 One hundred parts of the copoly-condensate obtained in Example3, 10 parts of Resimene 882 (a) butyrated melamine formaldehyde resinavailable from Monsanto Company), 5 parts of Epon 1001, a condensationproduct of epichlorohydrin and bisphenol-A (Shell Chemical Co.) and 30parts of a prepolyrner were mixed and applied to a glass plate. Thecoated film can be dried to finger touch dryness in 30 minutes and curedhard in 5 hours.

EXAMPLE Thirty parts of titanium dioxide, 50 parts of the reactionproduct of Example 1, and 20 parts of a prepolyrner of xylenediisocyanate were mixed and the mixture was applied to a glass plate.The coated film had a gloss of and a pencil hardness of 2H.

EXAMPLE 10 Forty parts of the copolymer obtained in Example 3, 20 partsof A inch cellulose acetate butyrate, 10 parts of xylene diisocyanateprepolyrner, and 30 parts of titanium dioxide were mixed, and with theaddition of a suitable amount of solvent, the whole mixture was appliedto a glass plate. A good coated film having a pencil hardness of 2H anda high gloss was formed.

EXAMPLE l l bond and at least one group selected from OH,

==c .s A. bond and anhydrides thereof C. a co-condensable monomerselected from the group consisting of compounds which contain a CC Igroup and are free of groups;alkyl esters of a,fi-unsaturated acids; andcompounds which contain a (like CONH,, CONl-lCl-l,Ol-l, CON(CH,OH orester groups in a ratio which is in the range of A 0.5 to 70 percent byweight B =0.5 to 60 percent by weight and C== lO0(A+B) percent byweightand b. a diisocyanate selected from the group consisting of xylenediisocyanate and prepolymers thereof.

2. A composition as in claim 1 wherein A is Z-hydroxy ethyl acrylate, Bis acrylic acid and C is a mixture of methyl methacrylate, ethylacrylate, ethyl hexyl acrylate and butyl methacrylate.

3. A composition as in claim 1 wherein A is a mixture of acrylamide,propylene glycol monoacrylate and Z-hydroxyethyl acrylate, B is acrylicacid and C is a mixture of styrene, ethyl acrylate and butylmethacrylate.

' 4. A composition as in claim 1 wherein A is a mixture of 2-hydroxypropyl acrylate and glycidyl methacrylate, B is maleic anhydrideand C is a mixture of acrylonitrile, ethyl acrylate,

methyl methacrylate and cyclohexyl methacrylate.

2. A composition as in claim 1 wherein A is 2-hydroxy ethyl acrylate, Bis acrylic acid and C is a mixture of methyl methacrylate, ethylacrylate, ethyl hexyl acrylate and butyl methacrylate.
 3. A compositionas in claim 1 wherein A is a mixture of acrylamide, propylene glycolmonoacrylate and 2-hydroxyethyl acrylate, B is acrylic acid and C is amixture of styrene, ethyl acrylate and butyl methacrylate.
 4. Acomposition as in claim 1 wherein A is a mixture of 2-hydroxypropylacrylate and glycidyl methacrylate, B is maleic anhydride and C is amixture of acrylonitrile, ethyl acrylate, methyl methacrylate andcyclohexyl methacrylate.